CN112108348B - Preparation method of graphical material - Google Patents
Preparation method of graphical material Download PDFInfo
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- CN112108348B CN112108348B CN202011008282.1A CN202011008282A CN112108348B CN 112108348 B CN112108348 B CN 112108348B CN 202011008282 A CN202011008282 A CN 202011008282A CN 112108348 B CN112108348 B CN 112108348B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/061—Special surface effect
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/107—Post-treatment of applied coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2507/00—Polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2507/00—Polyolefins
- B05D2507/01—Polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2602/00—Organic fillers
Abstract
A preparation method of a graphical material comprises the following preparation steps: s1, coating, namely coating a water-insoluble polymer on the substrate once, and then forming a single-layer coating layer through soft baking; or, coating the water-insoluble polymer on the substrate at least twice, and soft-baking after each coating to form a laminated coating layer; the polymer contains a protecting group; s2, printing, namely printing an acid-containing solution to a reaction area on the coating layer, wherein the reaction area corresponds to an area which does not need to be reserved in the graphical material; s3, heating, namely heating the acid-containing solution and the polymer in the reaction zone until the polymer in the reaction zone is easily dissolved in water after the protective group is lost; and S4, developing, soaking the polymer without the protective group in the reaction area into a developing solution, and forming a patterned material by the coating layer. Compared with the prior art, the method provided by the invention can reduce the preparation cost of the graphical material and improve the preparation stability, and has high universality.
Description
Technical Field
The invention relates to the field of semiconductors, in particular to a preparation method of a graphical material.
Background
In the semiconductor field, a patterning material is a critical functional material for realizing pattern transfer onto a substrate, and is generally made of photoresist by photolithography. In the prior art, compared with the conventional photolithography, the chemical amplification photolithography has the advantage of improving the quantum efficiency of the photoresist, and thus, more and more attention is paid to the chemical amplification photolithography.
In chemical amplification lithography, the main components of the photoresist are a polymer, a photoacid generator, and corresponding additives and solvents. The polymer is insoluble in water due to the resin having the protecting group. After the photoresist in the reaction area is exposed, the photoacid generator in the reaction area can generate an acidic substance, and the acidic substance is used as a chemical catalyst to remove a protecting group on a polymer during heat treatment, so that the photoresist in the reaction area is changed from being insoluble in a developing solution to being easily soluble in the developing solution, and the transfer of a pattern is realized. However, the prior art has certain disadvantages. First, the chemical amplification lithography process requires the use of lithography equipment for the exposure process, which requires high equipment and costs. Secondly, in the chemical amplification lithography, the lithography effect involves many factors, including the components and the ratio of the photoresist, the influence of exposure parameters on acidic substances, the influence of thermal treatment on the catalytic effect of acidic substances, etc. Under the superposition effect of various factors, the stable and reliable photoetching effect is difficult to realize in practice.
In view of the above, the present invention provides a method for preparing a patterning material, which can reduce the preparation cost of the patterning material and improve the preparation stability.
Disclosure of Invention
The invention provides a preparation method of a graphical material, and aims to reduce the preparation cost of the graphical material and improve the preparation stability.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the graphical material is innovative in that: the preparation method comprises the following preparation steps: s1, coating, namely coating a water-insoluble polymer on the substrate once, and then forming a single-layer coating layer through soft baking; or, coating the water-insoluble polymer on the substrate at least twice, and soft-baking the substrate after each coating to form a laminated coating layer; the polymer contains a protecting group; s2, printing, namely printing an acid-containing solution to a reaction area on the coating layer, wherein the reaction area corresponds to an area which does not need to be reserved in the graphical material; s3, heating, namely heating the acid-containing solution and the polymer in the reaction zone until the polymer in the reaction zone is easily dissolved in water after the protective group is lost; and S4, developing, soaking the polymer without the protective group in the reaction area into a developing solution, and forming a patterned material by the coating layer.
The relevant content in the above technical solution is explained as follows:
1. in this embodiment, the "patterning material" is used to provide a masking function in one or more subsequent steps.
2. In this embodiment, preferably, in step S1, the polymer applied each time is any one of polyhydroxystyrene, polystyrene, polymethacrylate, and polynorbornene containing a protecting group.
3. In this embodiment, the protecting group is any one of 4-t-butyloxycarbonyl, t-butyl acrylate and acetal.
4. In this aspect, the thickness of the coating layer is preferably 3um to 60 um.
5. In this aspect, preferably, the acid-containing solution includes any one or more of an organic acid, an inorganic acid, and an acidic solution. As a further preferred, the acid-containing solution contains, for example, any one or more of acrylic acid, methacrylic acid, acrylic ester, hexafluorophosphoric acid, norbornene carboxylic ester, tricyclodecene carboxylic ester and tetracyclodecene carboxylic ester. As a further preference, the pH value of the acid-containing solution is in the range of 0 to 5.
6. In this embodiment, the developer of the developing solution in step S4 preferably includes one or more of a quaternary ammonium solution and an alcohol amine solution.
7. In this embodiment, preferably, the developing solution in step S4 is an alkaline developing solution, and the alkaline developing solution contains any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
8. In this embodiment, in step S1, the coating layer of the laminate is preferably applied by spraying.
The beneficial effects of the invention are as follows.
Compared with the existing chemical amplification photoetching method, the preparation method of the graphical material can realize the preparation of the graphical material without an exposure step, and does not need corresponding photoetching equipment, so that the equipment requirement and the cost can be greatly reduced.
Secondly, compared with the existing chemical amplification photoetching method, the coating layer of the invention uses the polymer with simple components to replace the photoresist with complex component proportion, and uses the acid-containing solution to directly print instead of the prior art that the photo-acid generator generates acid substances and excites the catalytic effect by exposure and heat treatment. In contrast, the influence factors of the technical effect of the invention are relatively few and simple, so that the stability of the preparation of the graphical material can be effectively improved.
In addition, the method for preparing the patterned material provided by the invention is not only suitable for preparing a single-layer coating layer, but also suitable for preparing a laminated coating layer, and has higher universality, particularly has higher requirements on the thickness of the coating layer, the masking effect of the patterned material, the adhesion of the coating layer on a substrate, the reaction rate of the coating layer when the coating layer is heated in an acid-containing solution and the like.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a patterned material according to a first embodiment of the present invention;
fig. 2 is a process flow diagram of a method for preparing a patterned material according to a second embodiment of the present invention.
In the above drawings: 1. a substrate; 2. a coating layer; 3. a first coating layer; 4. a second coating layer; 5. a reaction zone; 6. an acid-containing solution; 7. the material is patterned.
Detailed Description
The invention is further described with reference to the following figures and examples:
the first embodiment is as follows:
referring to fig. 1, a method for preparing a patterned material using a single crystal silicon wafer with a <100> crystal orientation as a substrate 1 includes the following steps:
s1, coating, as shown in fig. 1 (a), a water-insoluble polymer is coated on the substrate 1 once, and then soft-baked at 50 ℃ to form a single coating layer 2; the polymer is polyhydroxystyrene containing a protective group. The protecting group is tert-butyl acrylate. The thickness of coating layer 2 is 3 um. In the present embodiment, the coating method is spin coating, but the present invention is not limited thereto, and related technical solutions applicable to other coating methods of the present invention, such as dip coating, roller coating, film coating, spray coating, blade coating, electrostatic coating, and screen printing, should also fall within the scope of the present invention, which is easily understood and accepted by those skilled in the art.
S2, printing, as shown in fig. 1 (b), an acid-containing solution 6 containing acrylic acid is printed onto the reaction areas 5 on the coating layer 2, the reaction areas 5 corresponding to areas of the patterning material 7 that are not to be retained. In this example, the acid-containing solution 6 has a pH of 5.
S3, heating, as shown in figure 1 (c), heating the acid-containing solution 6 and the polymer in the reaction zone 5 to 80 ℃ until the polyhydroxystyrene containing tert-butyl acrylate in the reaction zone 5 loses the protecting group of tert-butyl acrylate and is easily dissolved in water.
S4, developing, as shown in fig. 1 (d), soaking the polymer with the protective group lost in the reaction area 5 into a developing solution, and forming the patterned material 7 on the coating layer 2. In this example, the developer of the developing solution was 0.2g/L of tetrabutylammonium hydroxide aqueous solution.
Example two:
referring to fig. 2, a method for preparing a patterned material using a single crystal silicon wafer with a <100> crystal orientation as a substrate 1 includes the following steps:
s1, coating, as shown in fig. 2 (a), a water-insoluble polymer is coated twice on a substrate 1, and after each coating, soft-baking is performed at 50 ℃ to form a laminated coating layer 2, and the laminated coating layer 2 includes a first coating layer 3 and a second coating layer 4. Wherein, the polymer for the first coating is polystyrene containing a protective group 4-tert-butyloxycarbonyl, and the first coating layer 3 is formed after soft baking. The polymer coated on the first coating layer 3 for the second time is polymethacrylate containing acetal as a protective group, and a second coating layer 4 is formed after soft baking. In the present embodiment, the thickness of the coating layer 2 is 60 um. The coating layer 2 is applied by spraying, but the invention is not limited thereto, and related technical solutions suitable for other coating methods of the invention, such as roller coating, knife coating, electrostatic coating, and silk screen, should also fall within the scope of the invention, which is easily understood and accepted by those skilled in the art.
S2, printing, as shown in fig. 2 (b), an acid-containing solution 6 containing hexafluorophosphoric acid is printed onto the reaction regions 5 on the coating layer 2, the reaction regions 5 corresponding to regions of the patterning material 7 which do not need to be retained. In this example, the pH of the acid-containing solution 6 was 2.5.
S3, heating, as shown in figure 2 (c), the acid-containing solution 6 and the polymer in the reaction zone 5 are heated at 100 ℃ until the polymer in the reaction zone 5 is easily dissolved in water after losing the protecting group.
S4, developing, as shown in fig. 2 (d), soaking the polymer with the protective group lost in the reaction area 5 into a developing solution, and forming the patterned material 7 on the coating layer 2. In this example, the developing solution was an alkaline developing solution containing NaOH 3%.
In example two, the polymers used for different stacks of coating layers of the stack are of different types, but the invention is not limited thereto, and the polymers used for different stacks of coating layers of the stack may also be the same, as will be readily understood and accepted by the skilled person.
In the above embodiments, the formed patterned material may be used as a mask for subsequent processes, such as but not limited to electroplating, chemical deposition, evaporation, etching, ion implantation, and metal stripping processes.
In the above embodiments, the substrate is a monocrystalline silicon wafer with a <100> crystal orientation, but the present invention is not limited thereto, and the substrate may be a monocrystalline silicon wafer with other crystal orientations, a polycrystalline silicon wafer, glass for manufacturing a thin film solar cell, and the like, which are easily understood and accepted by those skilled in the art.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A preparation method of a graphical material is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s1, coating, namely coating a water-insoluble polymer on the substrate, and then soft-baking to form a single-layer coating layer; or, coating the water-insoluble polymer on the substrate at least twice, and soft-baking the substrate after each coating to form a laminated coating layer; the polymer contains a protecting group;
s2, printing, namely printing an acid-containing solution to a reaction area on the coating layer, wherein the reaction area corresponds to an area which does not need to be reserved in the graphical material;
s3, heating, namely heating the acid-containing solution and the polymer in the reaction zone until the polymer in the reaction zone is easily dissolved in water after the protective group is lost;
s4, developing, namely soaking the polymer without the protecting group in the reaction area into a developing solution, and forming a patterned material by the coating layer;
wherein, in step S1, the polymer coated each time is any one of polyhydroxystyrene, polystyrene, polymethacrylate and polynorbornene containing a protecting group; the protective group is any one of 4-tert-butyloxycarbonyl, tert-butyl acrylate and acetal;
wherein, the acid-containing solution contains any one or more of acrylic acid, methacrylic acid, acrylate, hexafluorophosphoric acid, norbornene carboxylic ester, tricyclodecene carboxylic ester and tetracyclodecene carboxylic ester.
2. The method for preparing a patterned material according to claim 1, wherein: the thickness of the coating layer is 3-60 μm.
3. The method for preparing a patterned material according to claim 1, wherein: the pH value range of the acid-containing solution is 0-5.
4. The method for preparing a patterned material according to claim 1, wherein: the developer of the developing solution in the step S4 includes one or more of a quaternary ammonium solution and an alcohol amine solution.
5. The method for preparing a patterned material according to claim 1, wherein: the developing solution in step S4 is an alkaline developing solution, and the alkaline developing solution contains any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
6. The method for producing a patterned material according to any one of claims 1 to 5, wherein: in step S1, the coating layer of the laminate is applied by spraying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011008282.1A CN112108348B (en) | 2020-09-23 | 2020-09-23 | Preparation method of graphical material |
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| CN202011008282.1A CN112108348B (en) | 2020-09-23 | 2020-09-23 | Preparation method of graphical material |
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| CN112108348A CN112108348A (en) | 2020-12-22 |
| CN112108348B true CN112108348B (en) | 2022-03-04 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008004735A1 (en) * | 2006-07-07 | 2008-01-10 | Cheil Industries Inc. | Micropattern-forming resin compositon and method for forming micropattern using the same |
| CN108257854A (en) * | 2017-09-27 | 2018-07-06 | 苏州太阳井新能源有限公司 | A kind of manufacturing method of patterned mask |
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- 2020-09-23 CN CN202011008282.1A patent/CN112108348B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008004735A1 (en) * | 2006-07-07 | 2008-01-10 | Cheil Industries Inc. | Micropattern-forming resin compositon and method for forming micropattern using the same |
| TW200813639A (en) * | 2006-07-07 | 2008-03-16 | Cheil Ind Inc | Micropattern-forming resin composition and method for forming micropattern using the same |
| CN108257854A (en) * | 2017-09-27 | 2018-07-06 | 苏州太阳井新能源有限公司 | A kind of manufacturing method of patterned mask |
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| CN112108348A (en) | 2020-12-22 |
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